Detector for SFC

Detection in SFC can be achieved in the condensed phase using optical detectors similar to those used in liquid chromatography or in the gas phase using detectors similar to those used in gas chromatography. Spectroscopic detectors, such as mass spectrometry and Fourier transform infrared spectroscopy, are relatively easily interfaced to SFC compared to the problems observed with liquid mobile phases (see Chapter 9). The range of available detectors for SFC is considered one of its strengths. 

A major advantage of Sl-C over FlPl.C is that the flame ionization detector (FID) of GC can be used. As discussed in Section 27B-4, the FID exhibits a general response to organic compounds, is highly sensitive, and is largely trouble free. Mass spectrometers are also more ea.sily adapted as detectors for. SFC than FlPl.C, Several of the detectors used in LC find use in SFC as well, including UV and IK absorption, fluorescence emission, thermionic, and flame photometric detectors. 

Mass Spectrometer Tuning. A three-step process was used to tune the quadrupole mass spectrometer prior to its use as a detector for SFC. In the first step, perfluorotributylamine (Pfaltz Bauer Inc., Stamford, Conn.) was ionized by electron ionization and used to calibrate the mass axis. In the second step, methane was introduced into the Cl source and the reagent ion profiles were optimized. In the third step, the mass resolution was adjusted for improved sensitivity. This was accomplished by introducing a volatile brominated compound, such as 2-bromopentane, into the Cl source. The mass spectrometer s resolving power was reduced such that the peaks... 

A powerful advantage of SFC is that more detectors can be interfaced with SFC than with any other chromatographic technique (Table 4.30). There are only a few detectors which operate under supercritical conditions. Consequently, as the sample is transferred from the chromatograph to the detector, it must undergo a phase change from a supercritical fluid to a liquid or gas before detection. Most detectors can be made compatible with both cSFC and pSFC if flow and pressure limits are taken into account appropriately. GC-based detectors such as FID and LC-based detectors such as UVD are the most commonly used, but the detection limits of both still need to be improved to reach sensitivity for SFC compatible with that in LC and GC. Commercial cSFC-FID became available in... 

Plasmas compare favourably with both the chemical combustion flame and the electrothermal atomiser with respect to the efficiency of the excitation of elements. The higher temperatures obtained in the plasma result in increased sensitivity, and a large number of elements can be efficiently determined. Common plasma sources are essentially He MIP, Ar MIP and Ar ICP. Helium has a much higher ionisation potential than argon (24.5 eV vs. 15.8 eV), and thus is a more efficient ionisation source for many nonmetals, thereby resulting in improved sensitivity. Both ICPs and He MIPs are utilised as emission detectors for GC. Plasma-source mass spectrometry offers selective detection with excellent sensitivity. When coupled to chromatographic techniques such as GC, SFC or HPLC, it provides a method for elemental speciation. Plasma-source detection in GC is dominated by GC-MIP-AES... 

As SFC provides gaseous sample introduction to the plasma and thus near-100 % analyte transport efficiency, coupling SFC with plasma mass spectrometry offers the potential of a highly sensitive, element-selective chromatographic detector for many elements. Helium high-efficiency microwave-induced plasma has been proposed as an element-selective detector for both pSFC and cSFC [467,468] easy hyphenation of pSFC to AED has been reported [213]. 

Another technique is supercritical fluid chromatography (SFC), which is a chromatographic technique that in many ways is a hybrid of GC and HPLC. It is recognized as a valuable technique for the analysis of thermolabile compounds, which would not be amenable to analysis by GC or HPLC. Few applications have been reported for SFC in the field of OCP and OPP determination (16). The advantages reported for SFC are versatility in separation (by the addition of modifier or the choice of stationary phase) and detection (with LC or GC detectors). However, SFC is a little-used technique because it still presents a wide range of instrumental problems (14-16). 

Several researchers have combined the separating power of supercritical fluid chromatography (SFC) with more informative spectroscopic detectors. For example, Pinkston et. al. combined SFC with a quadrupole mass spectrometer operated in the chemical ionization mode to analyze poly(dimethylsiloxanes) and derivatized oligosaccharides (7). Fourier Transform infrared spectroscopy (FTIR) provides a nondestructive universal detector and can be interfaced to SFC. Taylor has successfully employed supercritical fluid extraction (SFE)/SFC with FTIR dectection to examine propellants (8). SFC was shown to be superior over conventional gas or liquid chromatographic methods. Furthermore, SFE was reported to have several advantages over conventional liquid solvent extraction (8). Griffiths has published several... 

Pure fluids. Carbon dioxide is often the mobile phase of choice for SFC, since it has relatively mild critical parameters, is nontoxic and inexpensive, chemically inert, and is compatible with a wide variety of detectors including the flame ionization detector (FID) used widely in GC and the UV absorbance detector employed frequently in HPLC (7). The usefulness of carbon dioxide as a mobile phase in many instances is somewhat limited, however, because of its nonpolarity (8), and many polar compounds appear to be insoluble in it. For a sample containing polar compounds, pure carbon dioxide may not be the proper mobile phase. The elution of polar compounds is often difficult and the peak shapes for these polar compounds are sometimes poor. This latter difficulty is commonly observed with nonpolar supercritical fluids and may be due to active sites on the stationary phase rather than any inherent deficiency in the fluid itself. 

Figure 7.2.4 Experimental set-up used for SFC-NMR experiments (a) modifier pump (b) SFC pump (c) CO2 cylinder with dip-tube (d) cryostat (e) GC oven with mixing chamber and separation column (f) injection valve (g) UV detector (h) NMR magnet (i) backpressure regulator or restrictor (j) hardware control unit...

Figure 7.2.8 shows the contour plot of one constituent of the phthalate separation. Here the dead volume between the UV detector and the SFC flow cell was determined before the separation. After an adequate delay after the occurrence of the UV signal of bcnzyl-n-butylphthalate in the UV detector, the SFC separation was stopped and the two-dimensional acquisition was started. The pressure proved to be stable for several hours, which was sufficient for the acquisition of the two-dimensional COSY spectrum. Despite the intense... 

Microwave induced plasma mass spectrometry has also been used as a detector for supercritical fluid chromatography (SFC) [113] for the separation of halogenated hydrocarbons. The design of an SFC-MIP interface must ensure that the frit restrictor temperature remains at a high temperature to prevent condensation of analytes. Stainless steel transfer lines may be used. The frit restrictor should be connected to a length of deactivated fused silica capillary, inserted through the transfer line, and positioned flush with the aluminum MIP torch inset (Fig. 10.21). 

Fig. 7.15. Coupled SFE-SFC system with dual detector for the total and individual analysis of a coating fibre extract. (Reproduced with permission of Springer-Verlag.)...

All detectors in GC and LC can be easily made useful for SFC. Basically, however, we can say that GC detectors are useful for capillary SFC, and LC detectors are useful for packed-column SFC. The most important and convenient features of SFC are that any detection sys-... 

The most popular detector for PAHs is the UV detector. The detection limit was 0.2-2.5 ppb for 16 PAHs. A diode-array detector was also used for PAHs in SFC, and the detection limit was reported to be as low as 0.4 ppb. Other detections used for PAHs include mass spetrometric, thermoionic, infrared, photoionization, sulfur chemiluminescence, and fluorescence detectors. 

One of the major advantages of SFC over HPLC (high-performance liquid chromatography) is its compatibility with the flame ionization detector (FID), a universal and sensitive detector for carbon compounds. Unfortunately, most modifiers used in SFC are incompatible with FID. Therefore, a search for polar modifiers that have less response to FID led to the use of water, formic acid, and formamide. These modifiers produce acceptably low background noise and enable the use of FID. Because both water and formic acid have poor solubilities in carbon dioxide, they have been used as modifiers at very low concentrations. However, the modifier effect is significant even at this low level. For example, when water or formic acid was used as modifiers, the resolution of free fatty acids was significantly improved. 

Most commercial ELSDs employ a standard or modified HPLC nebulizer (Venturi flow type). It was believed that this nebulizer was not necessary for SFC because nebulization of the SFC mobile phase is accomphshed by gas expansion in a restrictor which controls pressure and mobile-phase flow rates. To counter the cooling effects of CO2 decompression in the linear fused-silica restrictor and improve heat transfer, Nizery et al., using a Cunow Clichy Model DDL 10 detector, placed the restrictor tip into a heated brass ring and applied heat to a small section of tubing between the restrictor and the drift tube... 

Two other types of element-specific detector for nitrogen currently in use coupled to SFCs are the nitrogen phosphorus detector (NPD) and the thermal energy analyzer (TEA). The NPD uses a hot, catalytically active solid surface immersed in a layer of dissociated H2 and O2 to form electronegative N and P ions which are detected on a nearby electrode [2]. NPD has been shown to have broad application in SFC, especially in the agrochemical industry [3]. The TEA, as described by Fine et al. [4], uses low-temperature pyrolysis, followed by ozone-induced chemiluminescence, for the detection of compounds containing NO2 groups. The TEA has been used for the determination of tobacco-specific nitrosamines and explosives [5]. Both of these detectors require spedlic standards of the analytes of interest for quantitation... 

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